EP0605719A1 - Device for treating exhaust gas - Google Patents

Device for treating exhaust gas Download PDF

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Publication number
EP0605719A1
EP0605719A1 EP92917398A EP92917398A EP0605719A1 EP 0605719 A1 EP0605719 A1 EP 0605719A1 EP 92917398 A EP92917398 A EP 92917398A EP 92917398 A EP92917398 A EP 92917398A EP 0605719 A1 EP0605719 A1 EP 0605719A1
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EP
European Patent Office
Prior art keywords
reactor
catalyst
exhaust gases
external casing
pipe
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92917398A
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German (de)
French (fr)
Other versions
EP0605719B1 (en
EP0605719A4 (en
Inventor
Kunio Yoshida
Atsushi Tsutsumi
Yasufumi Sakakida
Kazuo 4-4-12 Kawajyu Tsutsumi
Tomoaki Takada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kawasaki Heavy Industries Ltd
Kawasaki Motors Ltd
Original Assignee
Kawasaki Heavy Industries Ltd
Kawasaki Jukogyo KK
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Publication date
Application filed by Kawasaki Heavy Industries Ltd, Kawasaki Jukogyo KK filed Critical Kawasaki Heavy Industries Ltd
Publication of EP0605719A1 publication Critical patent/EP0605719A1/en
Publication of EP0605719A4 publication Critical patent/EP0605719A4/en
Application granted granted Critical
Publication of EP0605719B1 publication Critical patent/EP0605719B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2839Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
    • F01N3/2846Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration specially adapted for granular supports, e.g. pellets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404Removing only nitrogen compounds
    • B01D53/9409Nitrogen oxides
    • B01D53/9431Processes characterised by a specific device
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/10Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2803Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28Construction of catalytic reactors
    • F01N3/2803Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2832Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support granular, e.g. pellets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023Details
    • B01J2208/027Beds
    • B01J2208/028Beds rotating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18Details relating to the spatial orientation of the reactor
    • B01J2219/182Details relating to the spatial orientation of the reactor horizontal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19Details relating to the geometry of the reactor
    • B01J2219/194Details relating to the geometry of the reactor round
    • B01J2219/1941Details relating to the geometry of the reactor round circular or disk-shaped
    • B01J2219/1946Details relating to the geometry of the reactor round circular or disk-shaped conical
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2290/00Movable parts or members in exhaust systems for other than for control purposes
    • F01N2290/02Movable parts or members in exhaust systems for other than for control purposes with continuous rotary movement
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2290/00Movable parts or members in exhaust systems for other than for control purposes
    • F01N2290/02Movable parts or members in exhaust systems for other than for control purposes with continuous rotary movement
    • F01N2290/06Movable parts or members in exhaust systems for other than for control purposes with continuous rotary movement driven by auxiliary drive
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00Structure of catalyst support or particle filter
    • F01N2330/08Granular material
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00Selection of materials for exhaust purification
    • F01N2370/02Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04Zeolitic material
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2470/00Structure or shape of gas passages, pipes or tubes
    • F01N2470/18Structure or shape of gas passages, pipes or tubes the axis of inlet or outlet tubes being other than the longitudinal axis of apparatus
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01NGAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2470/00Structure or shape of gas passages, pipes or tubes
    • F01N2470/22Inlet and outlet tubes being positioned on the same side of the apparatus
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00Engines characterised by air compression and subsequent fuel addition
    • F02B3/06Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention relates to an apparatus for processing exhaust gases, such as the gases exhausted from a diesel engine.
  • Denitrifying and soot-removing apparatuses for removing nitrogen oxides (NOx), soot and dust from within exhaust gases such as those from diesel engines are well known. These denitrifying and soot-removing apparatuses are designed to pass the exhaust gases through charged catalytic bed in order to remove the NOx by catalytic reactions.
  • Known examples of such denitrifying apparatuses are stationary catalytic bed reactors and gravity-fed catalytic fluidized bed reactors (such as that disclosed in Japanese Patent Application Laid-Open No. 52-131, 970).
  • a stationary catalytic bed reactor has a problem in that the reaction chamber becomes clogged with the soot and dust contained in the exhaust gases, which drastically impedes the processing efficiency thereof, and it is impossible to change the catalyst during operation when it becomes deteriorated.
  • a gravity-fed catalytic fluidized bed reactor has a problem in that it is inconvenient because it cannot respond to variations in exhaust gas quantity caused by variations in engine load and in that, in order to obtain a gas speed high enough to fluidize the catalyst, a distribution plate thereof must be made to have a large area, so that the size of the apparatus itself increases.
  • an object of the present invention is to provide an apparatus for processing exhaust gases that is designed to achieve a high fluidizing gas speed, increase the amount of exhaust gas that is processed, and have smaller overall dimensions.
  • the apparatus for processing exhaust gases in accordance with the present invention comprises an external casing having an introduction pipe for a gas being processed, such as exhaust gases, a circular cylindrical catalytic fluidized bed reactor provided in an internal portion of the external casing.
  • the interior of the reactor has a distributer formed of a multiply perforated cylinder for the introduction of the gases being processed, the multiply perforated cylinder being rotatably driven about a central axis thereof and containing a particulate catalyst, and the reactor is connected coaxially along that central axis to an exhaust pipe for the gases being processed, with the exhaust pipe protruding from the external casing.
  • FIG. 1 and FIG. 2 where reference number 1 denotes a catalytic fluidized bed reactor.
  • This reactor 1 has a multiply perforated circular cylinder 2.
  • the surface of this cylinder acts as a distribution plate or distributer, and end plates 3 and 4 are attached to both sides of the cylinder in the axial direction.
  • the outer surface at a central portion of one of these end plates 3 is fixed to a drive shaft 5, and a central portion of the other of the end plates 4 is fixed to one end of an exhaust pipe 6 having an axis that is the same as that of the drive shaft 5.
  • a particulate catalyst 7 is contained in the reactor 1.
  • a filter 8 of a circular cylindrical structure and having the same axis as the drive shaft 5 and the exhaust pipe 6 is fixed to the interior of the reactor 1. The filter 8 is provided to control the disposal of powdered catalyst 7 and dust.
  • the configuration is such that a pulley 9 is fixed to the drive shaft 5 and a rotational drive corresponding to the rotational speed of a diesel engine EG is transferred to the drive shaft 5 by a drive mechanism comprising, for example, a pulley 13 attached to a rotational shaft 12 of the engine EG and a drive belt 14.
  • An external casing 10 is provided surrounding the reactor 1.
  • the external casing 10 has a diameter greater than that of the reactor 1 and it is provided in such a manner that the entire reactor 1 and parts of the drive shaft 5 and the exhaust pipe 6 are covered thereby.
  • An exhaust gas introduction pipe 11 that is directly connected to an exhaust pipe 16 of the engine EG is provided on one side of the external casing 10.
  • the drive shaft 5 and the exhaust pipe 6 are supported so as to be free to rotate within the external casing 10 by bearings 17 and 18, respectively, of a sealed structure.
  • the reactor 1 and the external casing 10 are configured such that they can be disassembled to allow maintenance such as the exchange and/or cleaning of the catalyst 7 and filter 8.
  • the exhaust gases that have been cleaned by the denitrification reaction pass through the filter 8 and are released to the outside by the exhaust pipe 6.
  • a scraper 12 that is provided in frictional contact with the outer surface of the distributer 2, as shown in FIG. 4, is used to scrape off dust that adheres or attempts to adhere to the outer surface of the distributer 2, and the scraped-off dust collects in a dust reclamation portion 20 provided in a lower portion of the external casing 10.
  • the perforations 2a in the distributer 2 are formed to be of a comparatively large diameter so as to allow the passage of dust, dust will accumulate in the reactor 1. In such a case, the accumulated dust will react with and denitrify the exhaust gas.
  • a catalytic fluidized bed reactor 21 and an external casing 22 are connected in such a manner that the external casing 22 itself is made to rotate together with the reactor 21. Accordingly, as shown in the figure, one side of a distributer 23 that forms an outer circular cylindrical portion of the catalytic fluidized bed reactor 21 is fixed to one wall surface of the external casing 22.
  • Axial pipes 24 and 25 are formed at the centers of the two sides of the external casing 22, each outwardly directed, with one axial pipe 24 supported rotatably by a sealed axial bearing 27 on an exhaust gas introduction pipe 26 that is linked to the exhaust pipe of the engine.
  • the other axial pipe 25 is supported rotatably by a sealed axial bearing 28 on an exhaust pipe 29.
  • a pulley 30 for rotational drive is fixed to the axial pipe 24. Note that the operation of this embodiment performs a denitrification or dust removal, in the same manner as the embodiment shown in FIG. 1. Therefore, a detailed description thereof is omitted.
  • flow adjustment plates 32 are provided within a circular cylindrical filter 34 in the interior of a catalytic fluidized bed reactor 31, with these flow adjustment plates 32 being designed to reduce pressure losses in the apparatus.
  • the flow adjustment plates 32 have an annular shape and are fixed at an optimal spacing in the direction of the rotational axis of the apparatus.
  • the flow adjustment plates 32 are linked together by radial linkage plates 33.
  • Reference number 35 denotes an exhaust pipe.
  • the above described apparatus for processing exhaust gases can of course be used to provide dust removal, and it can also provide cracking chemical reactions such as denitrification, desulfurization, and de-salting, so it has a wide range of application.
  • FIG. 8 Another embodiment of the apparatus for processing exhaust gases in accordance with the present invention, which is provided with means for automatically supplying new catalyst and automatically removing deteriorated catalyst, is shown in FIG. 8.
  • This embodiment has a distributer 42 with a circular cylindrical surface, in the same way as previous embodiments, and is configured of a catalytic fluidized bed reactor 41 with end plates 43 and 44 fixed to each side thereof.
  • An axial pipe 45 is fixed to a central portion of one end plate 43 and a supply passage 45a for the catalyst 7 is formed integrally on the inner side of the axial pipe 45, perpendicular to the axis of the axial pipe.
  • One end of an exhaust pipe 47 whose axis matches that central axis of the axial pipe 45 is fixed to a central portion of the other end plate 44.
  • a circular cylindrical filter 48 is fixed to the inner side of the distributer 42, on the same axis as the axial pipe 45 and the exhaust pipe 47.
  • a hopper 44 for the catalyst 7 is provided in such a manner that a catalyst supply pipe 49 communicates therewith, and a catalyst reservoir 49a is formed integrally in a horizontal orientation at a lower portion of the catalyst supply pipe 49.
  • the above described axial pipe 45 is rotatably supported by a sealed bearing 50 on the catalyst reservoir 49a.
  • a discharge pipe 51 for the catalyst 7 is provided on one side of the end plate 44 remote from the supply passage 45a for the catalyst 7. The discharge pipe 51 opens into the fluidized bed of the catalyst 7.
  • An external casing 52 has a diameter greater than that of the reactor 41 and arranged in such a manner that the entire reactor 41 and parts of the exhaust pipe 47 and the catalyst reservoir 49a are covered thereby.
  • An exhaust gas introduction pipe 53 that is directly linked to an exhaust pipe (not shown in the figure) of the engine is provided on one side of the external casing 52.
  • a catalyst discharge passage 55 is formed in the portion of the external casing 52 on the end plate 44 side, isolated from the exhaust gas introduction side by an isolation plate 54, and the discharge pipe 51 for the catalyst 7 communicates with this catalyst discharge passage 55.
  • One end portion of the reactor 41 and a base portion of the exhaust pipe 47 are rotatably supported by bearings 56 and 57, respectively, in the isolation plate 54 and an outer plate 58 that forms part of the catalyst discharge passage 55.
  • the catalytic fluidized bed reactor 41 is rotatably supported at three points with respect to the external casing 52.
  • a pulley 60 is provided on the exhaust pipe 47 as means of rotatably driving the reactor 41.
  • This pulley 60 is connected to a drive transfer mechanism and a reduction mechanism, and thus a rotation corresponding to the speed of the engine is imparted to the reactor 41.
  • the exhaust gases that have been cleaned by the denitrification reaction pass through the filter 48 and are released to the outside by the exhaust pipe 47.
  • the perforations of the distributer 42 are of a diameter small enough that dust (such as unburnt carbon) is not trapped therein, dust that adheres or attempts to adhere to the outer surface of the distributer 42 can be scraped off by a scraper and collected in a dust reclamation portion provided in a lower portion of the external casing 52, in a similar manner to that shown in FIG. 4.
  • the perforations in the distributer 42 are formed to be of a comparatively large diameter so as to allow the passage of dust, dust will accumulate in the fluidized layer and this accumulated dust can react with and denitrify the exhaust gas.
  • the catalyst 7 in the catalyst reservoir 49a of the catalyst supply pipe 49 is supplied by centrifugal force into the fluidized bed through the supply passage 45a of the axial pipe 45. Catalyst 7 that has been degraded and powdered by the reaction flies out from the discharge pipe 51 and is reclaimed through the catalyst discharge passage 55.
  • a circular plate 61 of a diameter larger than that of the aperture of the axial pipe 45 is arranged on stays 59 facing the end plate 43, in place of the catalyst supply passage 45a of FIG. 8.
  • This construction ensures that the catalyst 7 flowing into the reactor 41 by the action of centrifugal force is supplied uniformly in the circumferential direction.
  • FIG. 10 A further modified embodiment shown in FIG. 10 is similar to that of FIG. 8, except that it is provided with a distributer 42a that has a tapered circular cylindrical shape. This ensures that the degraded, powdered catalyst 7 is discharged efficiently from the discharge pipe 51 by centrifugal force.
  • a distributer 42a that has a tapered circular cylindrical shape. This ensures that the degraded, powdered catalyst 7 is discharged efficiently from the discharge pipe 51 by centrifugal force.
  • structural components identical to those of FIG. 8 are given the same reference numbers and a detailed description of their structure is omitted.
  • the operation of components other than the distributer 42a are similar to those of the embodiment of FIG. 8 and hence description of their operation is also omitted.
  • a monocrystalline zeolite or a metal ion exchanger thereof such as a copper ion exchange zeolite (ZSM-5)
  • ZSM-5 copper ion exchange zeolite
  • a copper ion exchange zeolite is effective in the reduction of NOx in the exhaust gases from diesel engines.
  • a centrifugal fluidized bed of copper ion exchange zeolite is effective in the removal of powder and soot simultaneously with the reduction of NOx.
  • the zeolite (ZSM-5) could be synthesized by a hot water reaction. After filtration, particles of the ZSM-5 type of zeolite are suspended in water, copper (II) acetate is added thereto, and ion exchange processing takes place over 24 hours at room temperature. Next the zeolite particles are washed in distilled water, then dried at 383 K for 12 hours.
  • the composition of this zeolite is listed in Table 1.
  • a colloid of silica (20% by weight) is used as a binder for the catalyst, which is a copper ion exchange zeolite ZSM-5 obtained by spray-granulation, and this is sintered at 773K for four hours.
  • the physical characteristics of the catalyst obtained in this manner are listed in Table 2.
  • Table 1 Composition of Zeolite Cu ZSM-5 SiO2 [wt%] Al2O3 [wt%] Na2O [wt%] CuO [wt%] Firing Loss [wt%] Exchange Level [%] 84.7 4.9 1.3 3.2 3.2 65.8 Table 2 Physical Characteristics of Catalyst Average Particle Size [ ⁇ m] Density [kgm ⁇ 3] Void Ration [-] 26 1900 0.56
  • the catalyst could also be spherical particles obtained by spray-granulation of compounds containing silica sols and fine catalytic particles selected from a group consisting of metal carrying zeolites, metal silicates, and perovskite types of oxides.
  • the present invention is particularly applicable to the processing of exhaust gases from a diesel engine, but it can also be applied to the processing of various types of exhaust gas, depending on the choice of catalyst.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Toxicology (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Filtering Of Dispersed Particles In Gases (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

A fluid catalyst reactor (1, 21, 31 or 41) is rotatably provided in an outer casing (10, 22 or 52) having an untreated gas introducing pipe (11, 26 or 53) to receive exhaust from the diesel engine (EG). The reactor is driven by the diesel engine (EG). The reactor is filled with powdery catalyst (7) such as zeolite and catalyst (7) sticks to the inner peripheral wall of a cylindrical porous dispersing plate (2, 23, 42 or 42a) of the reactor with the rotation of the reactor and forms a fluidized layer while fluidized by untreated gas flowing inward in the radial direction from the inside of the outer casing into the reactor. Untreated gas having flowed into the reactor is treated with catalyst (7), passes a cylindrical filter (8, 34, or 48), and is exhausted through an exhaust pipe (6, 29, 35 or 47). Catalyst (7) reduces NOx gas in untreated gas. The fluidized catalyst layer is maintained by a strong centrifugal force acting thereon even though flowing speed of untreated gas into the reactor is high, whereby the flow quantity of untreated gas can be made large with the size of treating device reduced.

Description

    TECHNICAL FIELD
  • The present invention relates to an apparatus for processing exhaust gases, such as the gases exhausted from a diesel engine.
  • BACKGROUND ART
  • Denitrifying and soot-removing apparatuses for removing nitrogen oxides (NOx), soot and dust from within exhaust gases such as those from diesel engines are well known. These denitrifying and soot-removing apparatuses are designed to pass the exhaust gases through charged catalytic bed in order to remove the NOx by catalytic reactions. Known examples of such denitrifying apparatuses are stationary catalytic bed reactors and gravity-fed catalytic fluidized bed reactors (such as that disclosed in Japanese Patent Application Laid-Open No. 52-131, 970).
  • However, a stationary catalytic bed reactor has a problem in that the reaction chamber becomes clogged with the soot and dust contained in the exhaust gases, which drastically impedes the processing efficiency thereof, and it is impossible to change the catalyst during operation when it becomes deteriorated.
  • A gravity-fed catalytic fluidized bed reactor has a problem in that it is inconvenient because it cannot respond to variations in exhaust gas quantity caused by variations in engine load and in that, in order to obtain a gas speed high enough to fluidize the catalyst, a distribution plate thereof must be made to have a large area, so that the size of the apparatus itself increases.
  • Therefore, an object of the present invention is to provide an apparatus for processing exhaust gases that is designed to achieve a high fluidizing gas speed, increase the amount of exhaust gas that is processed, and have smaller overall dimensions.
  • DISCLOSURE OF THE INVENTION
  • To achieve the above objective, the apparatus for processing exhaust gases in accordance with the present invention comprises an external casing having an introduction pipe for a gas being processed, such as exhaust gases, a circular cylindrical catalytic fluidized bed reactor provided in an internal portion of the external casing. The interior of the reactor has a distributer formed of a multiply perforated cylinder for the introduction of the gases being processed, the multiply perforated cylinder being rotatably driven about a central axis thereof and containing a particulate catalyst, and the reactor is connected coaxially along that central axis to an exhaust pipe for the gases being processed, with the exhaust pipe protruding from the external casing.
  • BRIEF DESCRIPTION OF THE DRAWINGS
    • FIG. 1 is a cross sectional view, taken in the axial direction, of one embodiment of an apparatus for processing exhaust gases in accordance with the present invention;
    • FIG. 2 is a cross sectional view taken along the line II-II in FIG. 1;
    • FIG. 3 is a perspective view showing the relationship between a diesel engine and the apparatus for processing exhaust gases;
    • FIG. 4 is a cross sectional view of a modification of the embodiment of FIG. 1, taken in the axial direction;
    • FIG. 5 is a cross sectional view of another embodiment of the present invention, taken in the axial direction;
    • FIG. 6 is a cross sectional view of a further embodiment of the present invention, taken in the axial direction;
    • FIG. 7 is a cross sectional view taken along the line VII-VII in FIG. 6;
    • FIG. 8 is a cross sectional view of yet another embodiment of the present invention, taken in the axial direction;
    • FIG. 9 is a cross sectional view of a modification of the embodiment of FIG. 8, taken in the axial direction; and
    • FIG. 10 is a cross sectional view of another modification of the embodiment of FIG. 8, taken in the axial direction.
    BEST MODE FOR CARRYING OUT THE INVENTION
  • Embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
  • The description will first deal with an embodiment shown in FIG. 1 and FIG. 2 where reference number 1 denotes a catalytic fluidized bed reactor. This reactor 1 has a multiply perforated circular cylinder 2. The surface of this cylinder acts as a distribution plate or distributer, and end plates 3 and 4 are attached to both sides of the cylinder in the axial direction. The outer surface at a central portion of one of these end plates 3 is fixed to a drive shaft 5, and a central portion of the other of the end plates 4 is fixed to one end of an exhaust pipe 6 having an axis that is the same as that of the drive shaft 5. A particulate catalyst 7 is contained in the reactor 1. A filter 8 of a circular cylindrical structure and having the same axis as the drive shaft 5 and the exhaust pipe 6 is fixed to the interior of the reactor 1. The filter 8 is provided to control the disposal of powdered catalyst 7 and dust.
  • As shown also in FIG. 3, the configuration is such that a pulley 9 is fixed to the drive shaft 5 and a rotational drive corresponding to the rotational speed of a diesel engine EG is transferred to the drive shaft 5 by a drive mechanism comprising, for example, a pulley 13 attached to a rotational shaft 12 of the engine EG and a drive belt 14.
  • An external casing 10 is provided surrounding the reactor 1. The external casing 10 has a diameter greater than that of the reactor 1 and it is provided in such a manner that the entire reactor 1 and parts of the drive shaft 5 and the exhaust pipe 6 are covered thereby. An exhaust gas introduction pipe 11 that is directly connected to an exhaust pipe 16 of the engine EG is provided on one side of the external casing 10. As shown in FIG. 1, the drive shaft 5 and the exhaust pipe 6 are supported so as to be free to rotate within the external casing 10 by bearings 17 and 18, respectively, of a sealed structure. The reactor 1 and the external casing 10 are configured such that they can be disassembled to allow maintenance such as the exchange and/or cleaning of the catalyst 7 and filter 8.
  • The operation of the above embodiment will now be described. When the engine EG is started, the rotational drive thereof is transmitted through the drive transfer mechanism to drive the drive shaft 5. This rotates the catalytic fluidized bed reactor 1 together with the exhaust pipe 6 that is linked to the drive shaft 5, and the granular catalyst 7 contained within the reactor 1 is made to flow by centrifugal force so that it adheres to the inner surface of the distributer (the circular cylinder 2). At the same time that the engine EG starts, the exhaust gases therefrom are introduced through the exhaust gas introduction pipe 11 into the external casing 10 for the exhaust gas. These exhaust gases enter into the interior of the reactor 1 through perforations 2a in the distributer 2, propelled by the gas pressure of the engine EG, and the exhaust gases are brought into contact with the catalyst 7 while fluidizing the catalyst, to engender a reaction such as a denitrification reaction.
  • The exhaust gases that have been cleaned by the denitrification reaction pass through the filter 8 and are released to the outside by the exhaust pipe 6. If the perforations 2a of the distributer 2 are of a diameter small enough that dust (such as unburnt carbon) is not trapped therein, a scraper 12 that is provided in frictional contact with the outer surface of the distributer 2, as shown in FIG. 4, is used to scrape off dust that adheres or attempts to adhere to the outer surface of the distributer 2, and the scraped-off dust collects in a dust reclamation portion 20 provided in a lower portion of the external casing 10. Alternatively, if the perforations 2a in the distributer 2 are formed to be of a comparatively large diameter so as to allow the passage of dust, dust will accumulate in the reactor 1. In such a case, the accumulated dust will react with and denitrify the exhaust gas.
  • Another embodiment of the present invention will now be described with reference to FIG. 5. In this embodiment, a catalytic fluidized bed reactor 21 and an external casing 22 are connected in such a manner that the external casing 22 itself is made to rotate together with the reactor 21. Accordingly, as shown in the figure, one side of a distributer 23 that forms an outer circular cylindrical portion of the catalytic fluidized bed reactor 21 is fixed to one wall surface of the external casing 22. Axial pipes 24 and 25 are formed at the centers of the two sides of the external casing 22, each outwardly directed, with one axial pipe 24 supported rotatably by a sealed axial bearing 27 on an exhaust gas introduction pipe 26 that is linked to the exhaust pipe of the engine. The other axial pipe 25 is supported rotatably by a sealed axial bearing 28 on an exhaust pipe 29. A pulley 30 for rotational drive is fixed to the axial pipe 24. Note that the operation of this embodiment performs a denitrification or dust removal, in the same manner as the embodiment shown in FIG. 1. Therefore, a detailed description thereof is omitted.
  • In the embodiment of the present invention shown in FIG. 6 and FIG. 7, flow adjustment plates 32 are provided within a circular cylindrical filter 34 in the interior of a catalytic fluidized bed reactor 31, with these flow adjustment plates 32 being designed to reduce pressure losses in the apparatus. The flow adjustment plates 32 have an annular shape and are fixed at an optimal spacing in the direction of the rotational axis of the apparatus. The flow adjustment plates 32 are linked together by radial linkage plates 33. Reference number 35 denotes an exhaust pipe.
  • By selecting a suitable catalyst, the above described apparatus for processing exhaust gases can of course be used to provide dust removal, and it can also provide cracking chemical reactions such as denitrification, desulfurization, and de-salting, so it has a wide range of application.
  • Another embodiment of the apparatus for processing exhaust gases in accordance with the present invention, which is provided with means for automatically supplying new catalyst and automatically removing deteriorated catalyst, is shown in FIG. 8.
  • This embodiment has a distributer 42 with a circular cylindrical surface, in the same way as previous embodiments, and is configured of a catalytic fluidized bed reactor 41 with end plates 43 and 44 fixed to each side thereof. An axial pipe 45 is fixed to a central portion of one end plate 43 and a supply passage 45a for the catalyst 7 is formed integrally on the inner side of the axial pipe 45, perpendicular to the axis of the axial pipe. One end of an exhaust pipe 47 whose axis matches that central axis of the axial pipe 45 is fixed to a central portion of the other end plate 44. A circular cylindrical filter 48 is fixed to the inner side of the distributer 42, on the same axis as the axial pipe 45 and the exhaust pipe 47.
  • A hopper 44 for the catalyst 7 is provided in such a manner that a catalyst supply pipe 49 communicates therewith, and a catalyst reservoir 49a is formed integrally in a horizontal orientation at a lower portion of the catalyst supply pipe 49. The above described axial pipe 45 is rotatably supported by a sealed bearing 50 on the catalyst reservoir 49a. A discharge pipe 51 for the catalyst 7 is provided on one side of the end plate 44 remote from the supply passage 45a for the catalyst 7. The discharge pipe 51 opens into the fluidized bed of the catalyst 7.
  • An external casing 52 has a diameter greater than that of the reactor 41 and arranged in such a manner that the entire reactor 41 and parts of the exhaust pipe 47 and the catalyst reservoir 49a are covered thereby. An exhaust gas introduction pipe 53 that is directly linked to an exhaust pipe (not shown in the figure) of the engine is provided on one side of the external casing 52.
  • A catalyst discharge passage 55 is formed in the portion of the external casing 52 on the end plate 44 side, isolated from the exhaust gas introduction side by an isolation plate 54, and the discharge pipe 51 for the catalyst 7 communicates with this catalyst discharge passage 55. One end portion of the reactor 41 and a base portion of the exhaust pipe 47 are rotatably supported by bearings 56 and 57, respectively, in the isolation plate 54 and an outer plate 58 that forms part of the catalyst discharge passage 55. Thus the catalytic fluidized bed reactor 41 is rotatably supported at three points with respect to the external casing 52.
  • A pulley 60 is provided on the exhaust pipe 47 as means of rotatably driving the reactor 41. This pulley 60 is connected to a drive transfer mechanism and a reduction mechanism, and thus a rotation corresponding to the speed of the engine is imparted to the reactor 41.
  • The operation of the above embodiment will now be described. When the engine is started, the rotational drive thereof is transmitted through the reduction mechanism and the drive transfer mechanism to drive the exhaust pipe 47 and also rotate the catalytic fluidized bed reactor 41. The granular catalyst 7 contained within this reactor 41 is made to flow by centrifugal force so that it adheres to the inner surface of the distributer 42 and, at the same time that the engine starts, the exhaust gases therefrom are introduced through the exhaust gas introduction pipe 53 into the external casing 52. These exhaust gases enter into the interior of the reactor 41 through perforations in the distributer 42, propelled by the gas pressure of the engine, and the exhaust gases are brought into contact with the catalyst 7 while fluidizing the catalyst, to engender a reaction such as a denitrification reaction.
  • The exhaust gases that have been cleaned by the denitrification reaction pass through the filter 48 and are released to the outside by the exhaust pipe 47. If the perforations of the distributer 42 are of a diameter small enough that dust (such as unburnt carbon) is not trapped therein, dust that adheres or attempts to adhere to the outer surface of the distributer 42 can be scraped off by a scraper and collected in a dust reclamation portion provided in a lower portion of the external casing 52, in a similar manner to that shown in FIG. 4. Alternatively, if the perforations in the distributer 42 are formed to be of a comparatively large diameter so as to allow the passage of dust, dust will accumulate in the fluidized layer and this accumulated dust can react with and denitrify the exhaust gas.
  • The catalyst 7 in the catalyst reservoir 49a of the catalyst supply pipe 49 is supplied by centrifugal force into the fluidized bed through the supply passage 45a of the axial pipe 45. Catalyst 7 that has been degraded and powdered by the reaction flies out from the discharge pipe 51 and is reclaimed through the catalyst discharge passage 55.
  • In a modified embodiment shown in FIG. 9, a circular plate 61 of a diameter larger than that of the aperture of the axial pipe 45 is arranged on stays 59 facing the end plate 43, in place of the catalyst supply passage 45a of FIG. 8. This construction ensures that the catalyst 7 flowing into the reactor 41 by the action of centrifugal force is supplied uniformly in the circumferential direction. Note that structural components identical to those of the embodiment of FIG. 8 are given the same reference numbers and a detailed description of their structure is omitted. Note also that, since the operation of the components of this embodiment that are the same as those in FIG. 8 are similarly identical thereto, description of their operation is also omitted.
  • A further modified embodiment shown in FIG. 10 is similar to that of FIG. 8, except that it is provided with a distributer 42a that has a tapered circular cylindrical shape. This ensures that the degraded, powdered catalyst 7 is discharged efficiently from the discharge pipe 51 by centrifugal force. Note that structural components identical to those of FIG. 8 are given the same reference numbers and a detailed description of their structure is omitted. Note also that the operation of components other than the distributer 42a are similar to those of the embodiment of FIG. 8 and hence description of their operation is also omitted.
  • The effects obtained by the above described embodiments are described below.
    • (a) By allowing the catalytic fluidized bed reactor to rotate within an exhaust gas atmosphere, the catalytic fluidized bed can be made into a centrifugal fluidized bed. Therefore, forces always act in the radially outward direction in the fluidized bed, and it is thus difficult for the fluidized catalyst to be entrained in the radially inward direction by the flow of exhaust gases. Consequently, large fluidized gas speeds can be achieved in comparison with a conventional gravity-fed fluidized bed, therefore greater amounts of exhaust gases can be processed, and thus the entire apparatus can be designed to be small enough to be mounted on an automobile so that pollution problems caused by exhaust gases can be solved in a sensible manner.
    • (b) Since the engine's rotational force is used as the drive source for the catalytic fluidized bed reactor, a quantity of exhaust gas corresponding to the rotational speed of the engine can be processed efficiently.
    • (c) The supply of new catalyst and the removal of degraded, powdered catalyst can be done automatically, so the reactor for exhaust gases provides extremely efficient denitrification.
  • As the catalyst contained within a catalytic fluidized bed reactor for processing a diesel engine's exhaust gases, a monocrystalline zeolite or a metal ion exchanger thereof, such as a copper ion exchange zeolite (ZSM-5), could be used. A copper ion exchange zeolite is effective in the reduction of NOx in the exhaust gases from diesel engines. A centrifugal fluidized bed of copper ion exchange zeolite is effective in the removal of powder and soot simultaneously with the reduction of NOx.
  • The zeolite (ZSM-5) could be synthesized by a hot water reaction. After filtration, particles of the ZSM-5 type of zeolite are suspended in water, copper (II) acetate is added thereto, and ion exchange processing takes place over 24 hours at room temperature. Next the zeolite particles are washed in distilled water, then dried at 383 K for 12 hours. The composition of this zeolite is listed in Table 1. A colloid of silica (20% by weight) is used as a binder for the catalyst, which is a copper ion exchange zeolite ZSM-5 obtained by spray-granulation, and this is sintered at 773K for four hours. The physical characteristics of the catalyst obtained in this manner are listed in Table 2. Table 1
    Composition of Zeolite Cu ZSM-5
    SiO₂ [wt%] Al₂O₃ [wt%] Na₂O [wt%] CuO [wt%] Firing Loss [wt%] Exchange Level [%]
    84.7 4.9 1.3 3.2 3.2 65.8
    Table 2
    Physical Characteristics of Catalyst
    Average Particle Size [µm] Density [kgm⁻³] Void Ration [-]
    26 1900 0.56
  • The catalyst could also be spherical particles obtained by spray-granulation of compounds containing silica sols and fine catalytic particles selected from a group consisting of metal carrying zeolites, metal silicates, and perovskite types of oxides.
  • INDUSTRIAL APPLICABILITY
  • The present invention is particularly applicable to the processing of exhaust gases from a diesel engine, but it can also be applied to the processing of various types of exhaust gas, depending on the choice of catalyst.

Claims (14)

  1. A device for processing exhaust gases, comprising:
       an external casing having an introduction pipe for a gas being processed;
       a circular cylindrical catalytic fluidized bed reactor provided in an internal portion of said external casing, said reactor having in the interior thereof a distributer formed of a multiply perforated cylinder for the introduction of said gases being processed, said perforated cylinder being rotatably driven about a central axis thereof and having in the interior thereof a particulate catalyst; and
       an exhaust pipe for said gases being processed, connected to said reactor coaxially along said central axis and protruding from said external casing.
  2. A device for processing exhaust gases according to claim 1, wherein said reactor has on one side thereof said exhaust pipe and on the other side thereof a rotational drive shaft coaxial with said exhaust pipe, with said drive shaft protruding from said external casing.
  3. A device for processing exhaust gases according to claim 2, wherein said drive shaft is connected to an engine for being driven by said engine, and an exhaust pipe of said engine is connected to said introduction pipe.
  4. A device for processing exhaust gases according to claim 1, wherein a circular cylindrical filter is provided within said reactor about said central axis thereof, and said exhaust pipe communicates with the interior of said circular cylindrical filter.
  5. A device for processing exhaust gases according to claim 1, wherein said exhaust pipe is supported to be free to rotate in a sealed bearing in said external casing.
  6. A device for processing exhaust gases according to claim 1, further comprising a scraper provided within said external casing, in frictional contact with an outer peripheral surface of said distributer of said reactor.
  7. A device for processing exhaust gases according to claim 1, wherein said external casing is fixed to said reactor and is arranged to be free to rotate with said reactor.
  8. A device for processing exhaust gases according to claim 7, wherein said introduction pipe of said external casing is arranged coaxially with said exhaust pipe and said introduction pipe functions as a rotational drive input shaft.
  9. A device for processing exhaust gases according to claim 4, further comprising annular flow adjustment plates fixed in the interior of said circular cylindrical filter, spaced along the direction of the central axial thereof.
  10. A device for processing exhaust gases according to claim 1, further comprising a catalyst supply pipe for supplying catalyst, provided so as to protrude through said external casing into said reactor.
  11. A device for processing exhaust gases according to claim 10, wherein an inner end of said catalyst supply pipe has a catalyst reservoir.
  12. A device for processing exhaust gases according to claim 1, wherein a catalyst discharge passage is provided in said external casing and catalyst discharge means communicating with said catalyst discharge passage is provided at a position radially outward from said reactor.
  13. A device for processing exhaust gases according to claim 1, wherein said distributer of said reactor is configured of a tapered circular cylinder.
  14. A device for processing exhaust gases according to claim 1, wherein said catalyst is a zeolite.
EP92917398A 1992-06-01 1992-06-01 Method for treating exhaust gas Expired - Lifetime EP0605719B1 (en)

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PCT/JP1992/000709 WO1993024207A1 (en) 1992-06-01 1992-06-01 Device for treating exhaust gas

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Cited By (12)

* Cited by examiner, † Cited by third party
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DE19728699A1 (en) * 1997-07-04 1999-02-11 Metallgesellschaft Ag Process for the catalytic reduction of nitrogen oxides
US6235247B1 (en) * 1997-12-04 2001-05-22 Thomas C. Maganas Apparatus for low temperature degradation of diesel exhaust and other incomplete combustion products of carbon-containing fuels
US6457552B2 (en) 2000-02-15 2002-10-01 Thomas C. Maganas Methods and apparatus for low back pressure muffling of internal combustion engines
WO2002089875A1 (en) * 2001-05-10 2002-11-14 Innovata Biomed Limited Powder deaggregation device
US6520287B2 (en) * 1997-12-04 2003-02-18 Maganas Oh Radicals, Inc. Methods and systems for low temperature cleaning of diesel exhaust and other incomplete combustion products of carbon-containing fuels
WO2003051503A2 (en) * 2001-12-17 2003-06-26 The University Of Western Ontario Apparatus for volumetric metering of small quantity of powder from fluidized beds
US6962681B2 (en) 1997-12-04 2005-11-08 Maganas Oh Radicals, Inc. Methods and systems for reducing or eliminating the production of pollutants during combustion of carbon-containing fuels
US7509798B2 (en) 2004-10-27 2009-03-31 Maganas Thomas C Methods and systems for safely operating a diesel engine in a methane-rich environment
EP2398581A2 (en) * 2009-02-20 2011-12-28 H R D Corporation System and method for gas reaction
US8283512B1 (en) 2011-10-05 2012-10-09 Maganas Thomas C Method and system for enhanced energy production from transforming, reducing and eliminating organic material and medical wastes
US8512215B2 (en) 2011-10-05 2013-08-20 Thomas C. Maganas Method for enhanced energy production from transforming, reducing and eliminating organic material and medical waste
US8512644B1 (en) 2012-08-01 2013-08-20 Thomas C. Maganas System for transforming organic waste materials into thermal energy and electric power

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19728699A1 (en) * 1997-07-04 1999-02-11 Metallgesellschaft Ag Process for the catalytic reduction of nitrogen oxides
US6235247B1 (en) * 1997-12-04 2001-05-22 Thomas C. Maganas Apparatus for low temperature degradation of diesel exhaust and other incomplete combustion products of carbon-containing fuels
US6520287B2 (en) * 1997-12-04 2003-02-18 Maganas Oh Radicals, Inc. Methods and systems for low temperature cleaning of diesel exhaust and other incomplete combustion products of carbon-containing fuels
US6962681B2 (en) 1997-12-04 2005-11-08 Maganas Oh Radicals, Inc. Methods and systems for reducing or eliminating the production of pollutants during combustion of carbon-containing fuels
US6457552B2 (en) 2000-02-15 2002-10-01 Thomas C. Maganas Methods and apparatus for low back pressure muffling of internal combustion engines
WO2002089875A1 (en) * 2001-05-10 2002-11-14 Innovata Biomed Limited Powder deaggregation device
WO2003051503A3 (en) * 2001-12-17 2004-02-19 Univ Western Ontario Apparatus for volumetric metering of small quantity of powder from fluidized beds
WO2003051503A2 (en) * 2001-12-17 2003-06-26 The University Of Western Ontario Apparatus for volumetric metering of small quantity of powder from fluidized beds
US7509798B2 (en) 2004-10-27 2009-03-31 Maganas Thomas C Methods and systems for safely operating a diesel engine in a methane-rich environment
EP2398581A2 (en) * 2009-02-20 2011-12-28 H R D Corporation System and method for gas reaction
EP2398581A4 (en) * 2009-02-20 2014-02-26 H R D Corp System and method for gas reaction
US8283512B1 (en) 2011-10-05 2012-10-09 Maganas Thomas C Method and system for enhanced energy production from transforming, reducing and eliminating organic material and medical wastes
US8512215B2 (en) 2011-10-05 2013-08-20 Thomas C. Maganas Method for enhanced energy production from transforming, reducing and eliminating organic material and medical waste
US8512644B1 (en) 2012-08-01 2013-08-20 Thomas C. Maganas System for transforming organic waste materials into thermal energy and electric power

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NO940318D0 (en) 1994-01-31
DE69228993D1 (en) 1999-05-27
EP0605719B1 (en) 1999-04-21
NO310911B1 (en) 2001-09-17
DE69228993T2 (en) 1999-12-02
KR0120837B1 (en) 1997-10-27
DK0605719T3 (en) 1999-10-25
NO940318L (en) 1994-03-02
WO1993024207A1 (en) 1993-12-09
EP0605719A4 (en) 1995-02-01

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